Synthesis and characterization of a new nanosorbent based on functionalized magnetic nanoparticles and its use in the determination of mercury by FI-CV-ETAAS

In this work, a new chelating sorbent which employs 1,5-bis(di-2-pyridil)methylene thiocarbohydrazide as the functional group and magnetic nanoparticles (MNPs) as its support (DPTH-MNP) was synthetized and characterized. The MNPs were prepared by coprecipitation of Fe+2 and Fe+3 with NH3 and then coated with silica in order to easily bind the support and the functionalizing molecule. The aim of the synthesis of this material is applying it as a solid-phase extracting agent and evaluating its potential for the extraction and pre-concentration of trace amounts of analytes present in biological and environmental samples with on-line methods. The MNPs’ magnetic core would allow overcoming the usual backpressure problems that happen in solid-phase extraction methods thanks to the possibility of immobilizing the MNPs by applying an external magnetic field. From the study of its adsorption capacity toward metal ions, mercury and antimony were the most retained. Thus, a flow injection solid phase extraction and cold vapor generation method for mercury determination based on the use of this new chelating nanosorbent was optimized. The greatest efforts were put into the reactor design to minimize compaction and loss of nanosorbent. The knotted reactor shown in Figure 1 was chosen as the best. Then, chemical and flow variables were optimized by Central composite designs (CCDs). The method developed has showed to be useful for the automatic pre-concentration and determination of mercury in environmental and biological samples. The determination was performed using electrothermal atomic absorption spectrometry (ETAAS). Under the optimum conditions, pH 5 and 120 s preconcentration time, the enrichment factor was 5.33; the detection limit (3σ) was 7.8 ng L-1; the determination limit (10σ) was 99 ng L-1; and the precisions (calculated for 10 replicate determinations at a 1 and 5 µg L-1 standards) were 1.7 and 1.9 % (RSD), respectively. Two linear calibration graphs were obtained, from the determination limits to 10 µg L-1 and from 10 to at least 50 µg L-1. From the comparison with other similar methods found in the bibliography, the detection limit and precisions calculated with our method were better. In order to evaluate the accurate and applicability of the method, the analysis of five certified samples LGC 6016 estuarine water, TMDA 54.4 fortified lake water, SRM 2976 mussel tissue, TORT-1 lobster hepatopancreas and DOLT-1 dogfish liver by standard addition and external calibration, were addressed. The results showed good agreement between the certified values, or added amounts of mercury, and the found concentrations. The method was successfully applied to the determination of mercury in sea-water samples collected in the Málaga Bay.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Decorative PVD coatings as an enviromentally clean alternative to chrome plating

The objective of this work is to conduct applied research and development to demonstrate yhat metal or ceramic coatings deposited by Physical Vapor Deposition (PVD)are equivalent or superior in peformance and are a cost-effective alternative to chrome plating in decorative applications. Chromium plating is comercially used to produce wear-resistant and decorative coatings, but the plating bath contains hexavalent chromium, which has adverse health and environmental effects. The present study describes and compares the mechanical and tribological properties of TiN,AlTiN, ZrCN coatings deposited by CAPVD (cathodic arc plasma pgysical vapor deposition), on nickel plated aluminium substrates. The properties of the above mentioned PVD coatings have been compared with the properties of conventional chromium plating.Peer Reviewe

Rapid Magnetic Dispersive solid phase extraction to preconcentration/determination of Cd and Pb in aqueous samples

A new magnetic dispersive solid phase extraction (MDSPE) method and graphite furnace atomic absorption spectrometry (GFAAS) have been combined for the analysis of Cd and Pb in environmental samples. For the preconcentration, a shell structured Fe3O4@graphene oxide nanospheres was synthetized and characterized. The material was suspended in the ionic liquid 1-n-butyl-3-metilimidazolium tetrafluoroborate [BMIM][BF4], the obtained stable colloidal suspension is named ferrofluid. GO presents excellent adsorbent properties for organic species due to the presence of the electronic π system. For this reason, the organic ligand [1,5-bis-(2-dipyridyl) methylene] thiocarbonohydrazide (DPTH) was used in order to form organic complexes of Cd and Pb. Once the DPTH ligand has been added to sample, the ferrofluid was injected and finely dispersed in the sample solution in order to extract the formed chelates. The complete adsorption of the chelates took place within few seconds then, the solid was separated from the solution with the aid of a strong magnet. Cd and Pb ions were desorbed from the material with 1 mL of acid nitric 5% solution and quantified by GFAAS. All experimental and instrumental variables were optimized. The analytical performances of the optimized method were: EF (Enrichment factor): 200 with LODs (detection limit): 0.005 and 0.004 µg L-1 and LOQs (determination limit): 0.017 and 0.013 µg L-1, for Cd and Pb, respectively. The reliability of the developed procedure was tested by relative standard deviation (% RSD), which was found to be < 5%. The accuracy of the proposed method was verified using certified reference materials (SLRS-5, SPS-SW2, and BCR-723) and by determining the analyte content in spiked aqueous samples. Sea waters and tap water samples collected from Málaga (Spain) were also analysed. The determined values were in good agreement with the certified values and the recoveries for the spiked samples were around 100% in all cases.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Cold vapour generation electrothermal atomic absorption spectrometry and solid phase extraction based on a new nanosorbent for sensitive HG determination in environmental samples (sea water and river water)

Reunión bianual del Grupo Regional Andaluz de la Sociedad Española de Química AnalíticaMercury is not an essential element for plant or animal life and it is a potential environmental toxic because of its tendency to form covalent bonds with organic molecules and the high stability of the Hg-C bond. Reports estimate a total mercury concentration in natural waters ranging from 0.2 to 100 ng L-1. Due to this fact, highly sensitive methods are required for direct determination of such extremely low levels. In this work, a rapid and simple method was developed for separation and preconcentration of mercury by flow injection solid phase extraction coupled with on-line chemical vapour generation electrothermal atomic absorption spectrometry. The system is based on chelating retention of the analyte onto the mini column filled with a mesoporous silica functionalized with 1,5 bis (di-2-pyridyl) methylene thiocarbohydrazide. The main aim of this work was to develop a precise and accurate method for the determination of the Hg. Under the optima conditions and 120 s preconcentration time, the detection limit obtained was 0.009 μg L-1, with RSDs 3.7 % for 0.2 μg L-1, 4.8 % for 1 μg L-1 and enrichment factor 4, Furthermore, the method proposed has permitted the determination of Hg with a reduction in the analysis time, the sample throughput was about 18 h-1, low consumption of reagents and sample volume. The method was applied to the determination of Hg in sea water and river water. For the quality control of the analytical performance and the validation of the newly developed method, the analysis of two certified samples, TMDA 54.4 Fortified Lake, and LGC6187 River sediment was addressed. The results showed good agreement with the certified values.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Determination of Pb using F3eO4 GO join to DPTH for ferrofluid based dispersive solid phase extraction

In this work has been described a green and rapid method the synthesis of Fe3O4@GO nanospheres via chemical covalent bonding method. The Fe3O4@GO DPTH was applied to ferrofluid based dispersive solid phase extraction of lead as a model analyte using an ionic liquid carrier. The ferro fluid allows the rapid extraction of lead ions using a low amount of sorbent material. Besides, the magnetic separation greatly improved the separation rate. The presented method is highly time saving due to the high dispersion of the sorbent in the aqueous phase and also there is no need to shake the sample solution. The other benefits of the proposed methods are simplicity of operation, low cost, high sorption capacity, high recovery and high preconcentration. In order to optimize the method the following parameters were studied: sample solution pH, concentration of DPTH, extraction time, amount of sorbent, desorption conditions, influence of ionic strength, and tolerance of potentially interfering ions. The sample or standard solution containing Pb(II), DPTH (0.05% ethanol w/v), NaCl (0.5 %, w/v) and buffer (pH = 5.6) was poured into high volume. Then 240 µL of ferrofluid was injected rapidly into the sample solution through a syringe. Thereupon, a dark cloudy suspension was formed, ferrofluid was dispersed thoroughly in solution and the complex of Pb-DPTH was extracted in a few seconds. Subsequently, a strong magnet was placed at the bottom of the tube to let the extractant settle. After about 3 min, the solution became clear and the supernatant was discarded simply by decanting it. Afterwards, the magnet was removed and 1 mL of nitric acid (2.0 mol L−1) was introduced to the vial to desorb the Pb by sonication. Finally, the sorbent was separated by positioning the magnet to the outside of the tube and the concentration of Pb in acidic aqueous phase was determined by ETAAS.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Forms and factors of deterioration of urban art murals under humid temperate climate; influence of environment and material properties

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGThis study describes the different alteration forms in 25 street art murals created between 2007 and 2018 on different substrates and located in different cities in NW Spain. The deterioration forms described affect the entire layer of the paintings as well as the substrates, with the most common being loss of colour (fading), loss of the pictorial layer -with or without loss of part of the substrate and biodeterioration. Physical, chemical, mineralogical and micromorphological analyses of samples from 10 murals revealed that (1) the deterioration mechanisms are related to environmental conditions and also to the inherent properties of the painting materials and to paint-substrate interaction, (2) the deterioration is closely associated with inherent aspects of urban art and (3) the loss of the pictorial record sometimes occurs in a very short period of time. The study findings highlight the need for preventive conservation measures in artworks (generally commissioned) that are intended to last

Efficacy of mechanical procedures for removal of a lichen and a gypsum black crust from granite

This paper provides preliminary data on the use of three different mechanical procedures to remove the lichen Diploschistes scruposus and a gypsum black crust from an ornamental granite. The methods used were wet sandblasting (Hydrogommage®), dry sandblasting (IBIX®) and dry-ice blasting. In addition, lichens were also removed by scraping with a scalpel. The cleaning efficacy and undesirable effects to granite were evaluated by stereomicroscopy, colour spectrophotometry, Fourier-transform infrared spectroscopy and scanning electron microscopy. The cleaning efficacy of the mechanical methods depended on the deposit being removed: i) for lichen, dry sandblasting and dry ice blasting produced the best results, while for the black gypsum crust, although both dry and wet sandblasting removed the black particulate matter from the crust, gypsum crystals remained on the surface; ii) the dry sandblasting method induced extraction of granite grains with the subsequent appearance of fissures; iii) for the lichen, the wet sandblasting method was totally unsatisfactory and iv) for the gypsum black crust, dry ice blasting failed to remove the black particulate matter from the crust.Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGMinisterio de Economía, Industria y Competitividad | Ref. IJCI-2017-327

Deterioration of graffiti spray paints applied on granite after a decade of natural environment

Graffiti spray paints are commonly used in contemporaneous mural paintings in public spaces, contributing to the transformation of sites and urban life. These outdoor artworks are now beginning to show different deterioration forms, such as physical-mechanical alteration (loss of material and cohesion, etc.) and chromatic changes. However, the deterioration has not been formally characterized, and the influence of the paint composition and underlying substrate are not known. In this study, three non-metallic (red, blue and black) alkyd graffiti spray paints and one metallic (silver) polyethylene graffiti spray paint were applied to two granite stones with different mineralogy and texture and exposed to a natural urban-marine environment near Vigo (NWSpain) for one decade (2010−2020). Physical changes were evaluated by stereomicroscopy, colour spectrophotometry, measurements of gloss, surface roughness and static contact angle, and peeling test. Mineralogical changes were determined by x-ray diffraction and molecular changes by Fourier transform infrared spectroscopy. Moreover, micromorphological and chemical characterization of the surfaces was conducted by scanning electron microscopy. Physical-mechanical changes, such as craquelure and paint loss, depended on the texture of the granite. More specifically, paint on the granite with the finest grain size showed most intense cracking and loss of material. Chemical changes, which were not related to the granite substrate, were most intense in the red and silver paint coatings. In the red paint, loss of binder was accompanied by an intense fading of the colour (due to titanium dioxide relative enrichment), while in the silver paint coating, chemical changes occurred in both the organic binder and aluminiumparticles, thus darkening the colour. Fewer chemical changes were observed in the blue and black paints. Physical and chemical changes detected in these paints were not correlated.Ministerio de Ciencia e Innovación | Ref. RYC2020-028902-IEuropean Commission | Ref. n. 588082-EPP-A-2017-1-IT-EPPKA2-K